US9780362B2 - Electrode having a selectively loaded matrix and method of manufacturing - Google Patents
Electrode having a selectively loaded matrix and method of manufacturing Download PDFInfo
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- US9780362B2 US9780362B2 US14/928,362 US201514928362A US9780362B2 US 9780362 B2 US9780362 B2 US 9780362B2 US 201514928362 A US201514928362 A US 201514928362A US 9780362 B2 US9780362 B2 US 9780362B2
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
- H01M4/80—Porous plates, e.g. sintered carriers
- H01M4/808—Foamed, spongy materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- This disclosure relates to an electrode having a selectively loaded matrix and methods of manufacturing the selectively loaded matrix and electrode.
- Hybrid vehicles (HEV) and electric vehicles (EV) use chargeable-dischargeable power sources.
- Secondary batteries such as lithium-ion batteries are typical power sources for HEV and EV vehicles.
- Lithium-ion secondary batteries typically use carbon, such as graphite, as the anode electrode.
- graphite materials are very stable and exhibit good cycle-life and durability. However, graphite material suffers from a low theoretical lithium storage capacity of only about 372 mAh/g. This low storage capacity results in poor energy density of the lithium-ion battery and low electric mileage per charge.
- silicon has been added to active materials.
- silicon active materials suffer from rapid capacity fade, poor cycle life and poor durability.
- One primary cause of this rapid capacity fade is the massive volume expansion of silicon (typically up to 300%) upon lithium insertion. Volume expansion of silicon causes particle cracking and pulverization. This deteriorative phenomenon escalates to the electrode level, leading to electrode delamination, loss of porosity, electrical isolation of the active material, increase in electrode thickness, rapid capacity fade and ultimate cell failure.
- Electrodes having a matrix selectively loaded with particular active particles.
- One embodiment of an electrode disclosed herein has a current collector, a separator and a matrix having first pores having a first size and second pores having a second size, the first size being larger than the second size, the second pores being uniformly distributed throughout the matrix; first active particles deposited in the first pores, the first active particles having a first particle size smaller than the first pores and larger than the second pores; and second active particles deposited in the second pores, the second active particles having a second particle size smaller than the second pores.
- One method of preparing an electrode having selectively loaded active materials as disclosed herein comprises preparing a first slurry of first active particles having a first particle size and a second slurry of second active particles having a second particle size; selectively depositing the first active particles in a matrix by pulling the matrix through the first slurry, the matrix including first pores having a first size and second pores having a second size, the first size being larger than the second size, the second pores being uniformly distributed throughout the matrix, wherein the first particle size of the first active particles is smaller than the first pores and larger than the second pores; drying the matrix deposited with the first active particles; selectively depositing the second active particles in the matrix by pulling the matrix through the second slurry; and drying the matrix deposited with the first active particles and the second active particles.
- FIG. 1 is a cross sectional view of an embodiment of an electrode as disclosed herein;
- FIG. 2 is a cross sectional view of another embodiment of an electrode as disclosed herein;
- FIG. 3 is a cross sectional view of another embodiment of an electrode as disclosed herein;
- FIG. 4 is a cross sectional view of another embodiment of an electrode as disclosed herein;
- FIG. 5 is a cross sectional view of another embodiment of an electrode as disclosed herein;
- FIG. 6 is a schematic of a matrix used in the electrodes disclosed herein;
- FIG. 7 is a schematic of the matrix illustrating partial active particle loading
- FIG. 8 is a flow diagram of a method of making the electrodes disclosed herein;
- FIG. 9 is a flow diagram of another method of making the electrodes disclosed herein.
- FIG. 10 is a flow diagram of additional method steps that can be included in the methods disclosed.
- FIG. 11 is a flow diagram of a method of making the matrix disclosed herein.
- the carbon material used in electrodes of conventional batteries such as lithium ion batteries or sodium ion batteries, suffers from a low specific capacity, the conventional battery has poor energy density even though there is small polarization and good stability. Furthermore, batteries having electrodes of graphite or other carbon materials develop increased internal resistance over time, which decreases their ability to deliver current.
- Silicon, tin, germanium and their oxides and alloys are non-limiting examples of materials that may be added to an electrode active material layer to improve its energy density, among other benefits.
- One particular example is the use of silicon in lithium-ion batteries.
- Silicon based anode active materials have potential as a replacement for the carbon material of conventional lithium-ion battery anodes due to silicon's high theoretical lithium storage capacity of 3500 to 4400 mAh/g. Such a high theoretical storage capacity could significantly enhance the energy density of the lithium-ion batteries.
- silicon active materials suffer from rapid capacity fade, poor cycle life and poor durability.
- volume expansion of silicon typically up to 300%) upon lithium insertion.
- Volume expansion of silicon can cause particle cracking and pulverization when the silicon has no room to expand. This expansion can lead to electrode delamination, electrical isolation of the active material, capacity fade due to collapsed conductive pathways, and, like carbon based electrodes, increased internal resistance over time, which decreases their ability to deliver current.
- Electrodes formed with matrices that can be selectively loaded to uniformly distribute different active catalyst particles across the active material layer. This uniform distribution assists in countering the effects of the volume expansion of active particles with high lithium storage capacity, including agglomeration of the active particles upon expansion and contraction.
- the matrix in which the active particles are loaded reduces delamination, retains conductive pathways and assists in overall extending the life of a battery incorporating the electrodes disclosed herein.
- FIGS. 1-4 illustrate embodiments of the electrode disclosed herein.
- the electrode 10 has a current collector 12 and a separator 14 . Between the current collector 12 and the separator 14 is an active material layer 16 having a matrix 20 , illustrated in FIG. 6 .
- the matrix 20 has first pores 22 having a first size and second pores 24 having a second size, the first size being larger than the second size, the second pores 24 being uniformly distributed throughout the matrix 20 .
- first active particles 26 are deposited in the first pores 22 , the first active particles 26 having a first particle size smaller than the first pores 22 and larger than the second pores 24 .
- Second active particles 28 are deposited in the second pores 24 , the second active particles 28 having a second particle size smaller than the second pores 24 .
- the active electrode layer 16 comprises the matrix 20 , the first active particles 26 and the second active particles 28 .
- Another embodiment of an electrode 30 is illustrated in FIG. 2 , in which the matrix 20 forms the current collector and the first active particles 26 and the second active particles 28 form the active material layer, forming a dual purpose layer 32 in the electrode 30 .
- FIG. 3 Another embodiment of an electrode 40 is illustrated in FIG. 3 , in which the dual purpose layer 32 of FIG. 2 includes a second active material layer 42 without a matrix layered onto the dual purpose layer 32 .
- the second active material layer 42 can have the same active particles used in the dual purpose layer 32 or can be different active particles.
- the first active particles 26 and second active particles 28 in the dual purpose layer 32 can be graphite and silicon, respectively, while the second active material layer 42 is graphite.
- FIG. 4 Another embodiment of an electrode 50 is illustrated in FIG. 4 , in which the active material layer 16 of FIG. 1 , layered on the current collector 12 , has the second active material layer 42 without a matrix layered onto the active material layer 16 .
- the second active material layer 42 can have the same active particles used in the active material layer 16 or can be different active particles.
- the first active particles 26 and second active particles 28 in the active material layer 16 can be graphite and silicon, respectively, while the second active material layer 42 is graphite.
- the current collector can comprise both the matrix within the active electrode layer 16 and the solid portion current collector 12 .
- FIG. 5 Another embodiment of an electrode 60 is illustrated in FIG. 5 , in which the active material layer 16 of FIG. 1 has a layer of matrix 20 without active particles between the active particle layer 16 and the current collector 12 , essentially extending the current collector 12 to the matrix layer 20 .
- Each of the electrode embodiments described can further include carbon black deposited in voids in the matrix 20 after deposition of the first active particles 26 and the second active particles 28 , along with a binder material. This ensures conductive contact between the active particles 26 , 28 .
- the binder material include polyamide, polyvinylidene fluoride, polytetrafluoroethylene, styrene-butadiene rubber and carboxymethyl cellulose.
- the electrodes herein can be used in any battery desired.
- the electrodes herein may be anodes in a lithium ion battery, with the first active particles 26 being graphite and the second active particles being silicon 28 .
- Other battery types and active material particles are contemplated.
- the matrix 20 can be a metal foam, such as a nickel foam or a copper foam.
- the matrix 20 can be selectively made to have a desired ratio of first pore size to second pore size as desired or required.
- the first pore size and/or the second pore size can be created uniformly throughout the matrix 20 , and concentrated regions and/or less concentrated regions can also be formed if desired or required.
- the matrix 20 can be made to have a single pore size or can be made to have more than two different pore sizes depending on the active particle loading desired or required.
- FIG. 11 is a flow diagram of one method of forming the matrix 20 .
- a layout is formed with first polymer beads of the first size, representing the first active particles 26 , and second polymer beads of the second size representing the second active particles 28 .
- first and second polymer beads can be used to form the layout.
- metal is deposited on the layout.
- the metal can be nickel or copper or another metal as desired or required.
- step S 14 the first polymer beads and the second polymer beads are dissolved with a solvent. The matrix is left behind with pores of the first size and the second size.
- FIG. 8 is a flow diagram of one of the methods herein.
- step S 20 a first slurry of first active particles 26 having a first particle size is prepared, and a second slurry of second active particles 28 having a second particle size is prepared.
- the first active particles 26 are selectively deposited in the matrix 20 by pulling the matrix 20 through the first slurry in step S 22 .
- the matrix 20 was made to include first pores 22 having a first size and second pores 24 having a second size, the first size being larger than the second size.
- the second pores 24 are uniformly distributed throughout the matrix 20 .
- the first particle size of the first active particles 26 in the first slurry is smaller than the first pores 22 and larger than the second pores 24 in the matrix 20 .
- the first active particles 26 get captured in the first pores 22 .
- the matrix 20 deposited with the first active particles 26 is then dried in step S 24 .
- step S 26 the second active particles 28 are selectively deposited in the matrix 20 by pulling the matrix 20 through the second slurry.
- the second particle size of the second active particles 28 in the second slurry is smaller than the second pore size of the matrix 20 . Accordingly, as the matrix 20 is pulled through the second slurry, the second active particles 28 are caught in the second pores 24 .
- the matrix 20 deposited with the first active particles 26 and the second active particles 28 is then dried in step S 28 .
- the method can further include the steps described in FIG. 9 . Note that identical steps between FIGS. 8 and 9 have the same reference numbers.
- a loading of the first active particles 26 in the first pores 22 can be determined in step S 30 .
- the desired loading of the first pores 22 with the first active particles 26 can be estimated by calculating the weight that the matrix 20 would be if a selected percent of the first pores 22 were loaded with the material of the first active particles 26 .
- the loaded matrix 20 can be weighed. If the weight of the matrix 20 is less than a predetermined weight that equates to a predetermined loading, not enough of the first pores 22 are filled with first active particles 26 .
- the method would move to step S 26 . If the weight of the matrix 20 indicated that less than ninety-six percent of the first pores 22 were filled, the method would repeat steps S 22 , S 25 and S 30 until the desired or required loading was obtained.
- a loading of the second active particles 28 in the second pores 24 can be determined in step S 32 as described above.
- the loading is less than a predetermined second loading, selectively depositing of the second active particles 28 in step S 26 , drying of the matrix in step S 28 and weighing of the matrix in step S 32 are repeated.
- the methods herein can further comprise preparing a third slurry of carbon black and a binder in step S 40 and pulling the matrix 20 through the third slurry to deposit the carbon black and the binder into voids of the matrix 20 from which the first active particles 26 and the second active particles 28 are absent.
- the methods and systems include a series of steps. Unless otherwise indicated, the steps described may be processed in different orders, including in parallel. Moreover, steps other than those described may be included in certain implementations, or described steps may be omitted or combined, and not depart from the teachings herein.
- the use of the term “collecting” is not meant to be limiting and encompasses both actively collecting and receiving data.
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2015
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